CN101234812A - Method for decoloring burned waste water by using zero-valent iron/ultrasonic wave synergistic reaction - Google Patents
Method for decoloring burned waste water by using zero-valent iron/ultrasonic wave synergistic reaction Download PDFInfo
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- CN101234812A CN101234812A CNA2008100103799A CN200810010379A CN101234812A CN 101234812 A CN101234812 A CN 101234812A CN A2008100103799 A CNA2008100103799 A CN A2008100103799A CN 200810010379 A CN200810010379 A CN 200810010379A CN 101234812 A CN101234812 A CN 101234812A
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Abstract
The invention relates to environmental chemistry, in particular to a method for decolorizing coking wastewater by using synergetic effect of zero-valent iron/ultrasonic waves, which specifically comprises the following steps: wastewater and zero-valent iron chips/powders are added into a reactor; the pH value of the wastewater is adjusted to be 1 to 6; then stirring is carried out under the effect of the ultrasonic waves with the power of 150 to 200W; the reaction is lasted for 30 to 60 minutes; the wastewater is decolorized and COD is removed. During the process, the use amount of zero-valent iron in each liter of wastewater is 2 to 500g, and the reaction temperature is 10 to 80 DEG C. By applying the method for decolorizing coking wastewater by using synergetic effect of zero-valent iron/ultrasonic waves, the chromaticity of the coking wastewater can drop from 1,500 times to 140 times, and the removal efficiency can reach over 90 percent; in addition, after the synergetic effect of the zero-valent iron and ultrasonic waves, the removal efficiency of COD in the coking wastewater is higher than the efficiency under the signal effect of the zero-valent iron and the ultrasonic waves. The obtained BOD5/COD is increased from 0.08 to 0.36, and the biodegradability of the wastewater is also increased remarkably.
Description
Technical field
The present invention relates to environmental chemistry, specifically a kind of method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction that coking chemical waste water is decoloured.
Background technology
Coking chemical waste water is the waste water that coal forms in the high temperature carbonization process and in the gas purification, chemical products treating process, wherein contain tens kinds of pollutents such as phenol, ammonia nitrogen, cyanogen, benzene, pyridine, indoles and quinoline, complicated component, Pollutant levels height, colourity height, toxicity are big, character is more stable, is a kind of trade effluent that typically contains the organic compound of difficult degradation.Easily biodegradable organics in the coking chemical waste water mainly is phenolic compound and benzene-like compounds, and arsenic is coughed up, naphthalene, furans, narrow azole and belong to the degradable type organic.The organism of difficult degradation mainly contains arsenic pyridine, carbazole, biphenyl, terphenyl etc.The discharging that exceeds standard of coking chemical waste water all can constitute very big harm to the mankind, aquatic products, farm crop.How to improve and solve the pollution problem of coking chemical waste water, become the problem that press for solution of pendulum in face of people environment.
Biological treatment is to utilize microbiological oxidation to decompose organic method in the waste water, the second-stage treatment in the Chang Zuowei coking wastewater processing system.At present, activated sludge process is a kind of most widely used coking chemical waste water aerobe treatment technology.This method is to allow biofloculation body and active sludge fully contact with organism in the waste water; Deliquescent organism is absorbed by cell and adsorbs, and finally to be oxidized to final product (mainly be CO
2).The non-solubility organism is converted into dissolved organic matter earlier, then by metabolism and utilization.But adopt this technology, the COD in the water outlet
Cr, BOD
5, NH
3Pollutent indexs such as-N all are difficult to up to standard, particularly to NH
3-N pollutent does not almost have Degradation.In recent years, people set about from microorganism, reactor and technical process several respects, have researched and developed biological reinforcing technology: biological fluidized bed, immobilization biological treatment technology and bio-denitrification technology etc.The development of these technology makes most of organic substances realize the biological degradation processing, and effluent quality has obtained very big improvement.
As a whole, biological process has advantages such as wastewater treatment capacity is big, process range is wide, working cost is relatively low.But the condition of water quality of the waste water of biological degradation method is strict: multiple factors such as the pH value of waste water, temperature, nutrition, toxic substance concentration, entering organic matter of water concentration, dissolved oxygen content all can have influence on growth and the effluent quality of bacterium in the mud, and this has also just proposed high requirement to operational administrative.In addition, through after the biochemical treatment, the colourity of coking chemical waste water does not almost change.In order further to reduce colourity, reach emission standard, through after the biochemical treatment, still to adopt some physics, chemical technology further to remove the colourity of coking chemical waste water and COD etc.
Iron is the active metal, and electropotential is E
0(Fe
2+/ Fe)=-0.440V, it has reducing power, can will arrange in metal replacement thereafter to come out and be deposited on the surface of iron, also ion that can oxidisability is stronger or compound and some organism reduction in metal activity command table.When being immersed in the composite grain of the cast iron that contains impurity or pure iron and charcoal in the aqueous solution, it is as follows that the numerous small galvanic cell electricity of formation is pulled reaction between iron and charcoal or other elements.
Anodic reaction: Fe 2e → Fe
2+E
0(Fe
2+/ Fe)=-0.440V;
Cathodic reaction: 2H
++ 2e → 2[H] → H
2↑ ... E
0(H
+/ H
2)=0.00V;
In recent years, the Zero-valent Iron removal, organism dechlorination etc. that are applied to groundwater pollutant are gradually polluted in the repair process.In addition, a handful of attempts removing by Zero-valent Iron the colourity of waste water.But owing to reasons such as temperature of reaction, pH control and iron passivation, the colourity of using Zero-valent Iron to remove waste water separately has significant limitation.The present invention will utilize cavitation effect of ultrasonic waves to eliminate the passivation of iron, and then improve the decolorizing effect of waste water.
Summary of the invention
The object of the invention is to provide a kind of method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction to waste water decoloring.
For achieving the above object, the technical solution used in the present invention is:
Method: waste water and zeroth order iron filings/powder are joined in the reactor, are stirring reaction 1-120min under the ultrasonic wave effect of 150-200W at power, realize that waste water decoloring and COD remove; The usage quantity of zeroth order iron powder is to add Zero-valent Iron 2-500g in every liter of waste water.
Described temperature of reaction is 10-80 ℃.The initial pH on wastewater value adopts hydrochloric acid to be adjusted to 1-6.Described Zero-valent Iron is an iron powder, and it can be micron order iron powder or nano grade iron powder, and micron order iron powder purity＞99%, particle diameter are 0.02～0.10mm, and specific surface area is 0.7～1.0m
2/ g; Nano grade iron powder, its purity＞99%, particle diameter are 30～100nm, specific surface area is 70～150m
2/ g.
The advantage that the present invention had:
The present invention utilizes in Zero-valent Iron/ultrasonic synergistic system, because ultrasonic cavitation, can produce oxidative free radical in the system, and the turbulence effect and the perturbation of solution are more violent simultaneously, promotes that zeroth order is iron acting to carry out.Experimental study shows that the particle diameter of Zero-valent Iron is more little, and removal effect is good more.Particle diameter small specific surface more is long-pending big more, and the ability of adsorbed gas is strong more, and water cavitation number of bubbles is many more; Surface-area is big more simultaneously, and the iron powder corrosion is fast more, just has more Fe
2+Generate.Two aspects all can improve the quantity of OH free radical in the water, strengthen the treatment effect of coking chemical waste water, improve the biodegradability of coking chemical waste water, significantly reduce the colourity of coking chemical waste water.
Adopt the present invention the colourity of waste water can be reduced to 140 times by initial 1500 times, clearance reaches more than 90%; In addition, after Zero-valent Iron and hyperacoustic synergy, the COD clearance of coking chemical waste water also acts on height separately than Zero-valent Iron, ultrasonic wave.The BOD of final outflow water
5/ COD brings up to 0.36 by original 0.08, and the biodegradability of waste water also obtains to significantly improve.
The present invention adopts the result of combined effects such as the reductive action of zero valent ferri treating polluted water, little electrolytic action, Coagulation and Adsorption effect: (1) iron is the active metal, have reducing power, thereby in acidic aqueous solution, can directly reducing dyes be become the amido organism.Look for lightly because of amido is organic, and easy oxidized decomposition is so the colourity in the waste water is minimized.Some heavy metal ion in the waste water also can be restored by iron, ion that other oxidisability are stronger or compound can by iron be reduced into toxicity less go back ortho states; (2) iron has electrochemical properties.[H] and [Fe of nascent state in the product of its electrode reaction
2+] can with many component generation redoxomorphismes in the waste water, can destroy the color development or the auxochromes of dyestuff, make it chain rupture, lose the color development ability.Also can make macromolecular substance be decomposed into micromolecular intermediate, perhaps make the chemical substance of some bio-refractory become the material of easy biochemical treatment, improve the biodegradability of water; Produce a large amount of Fe when (3) under the slant acidity condition, handling waste water
2+And Fe
3+,, can form Fe (OH) when pH transfers to alkalescence and aerobic when existing
2, and Fe (OH)
3Flocks, Fe (OH)
3Also may hydrolysis generate Fe (OH)
2 +, Fe (OH)
2+Deng complex ion, they all have very strong flocculating property.Original suspended substance in the waste water like this, and the insoluble substance that produces by little electrolysis and the insoluble substance that constitutes colourity all can be adsorbed cohesion, thus make sewage be able to further purification.
Description of drawings
Fig. 1 is ultrasonic wave of the present invention/Zero-valent Iron system synoptic diagram.
Main label is: 1. thermometer, 2 agitators, 3. reactor, 4. ultrasonic cleaner 5. zeroth order iron filings/powder.
Embodiment
Embodiment 1
1.0L waste water and 50g zeroth order iron powder are joined in the reactor, and wherein the character of Zero-valent Iron is: nano grade iron powder, and its purity＞99%, particle diameter are 35nm, specific surface area is 120m
2/ g; Adopting hydrochloric acid to regulate pH to 3.0, is stirring reaction 30min under 150W, the 30 ℃ of temperature at ultrasonic power then, realizes that waste water decoloring and COD remove (decolorizing effect is referring to table 1).
Table 1 ultrasonic wave/Zero-valent Iron collaboration system Treatment of Wastewater in Coking result relatively
| System/project | Water inlet COD | Water outlet COD | Water inlet colourity | Effluent color dilution | Water inlet BOD 5/COD | Water outlet BOD 5/COD |
| (mg/L) | (mg/L) | (doubly) | (doubly) | |||
| Zero-valent Iron acts on separately | 3240 | 2130 | 1500 | 1000 | 0.08 | 0.15 |
| Ultrasonic wave acts on separately | 3240 | 2860 | 1500 | 900 | 0.08 | 0.10 |
| The present invention | 3240 | 1260 | 1500 | 140 | 0.08 | 0.36 |
Adopt ultrasonic wave of the present invention/Zero-valent Iron synergy as known from Table 1, the colourity of waste water is reduced to 140 times by initial 1500 times, and clearance reaches more than 90%; In addition, after Zero-valent Iron and hyperacoustic synergy, the COD clearance of coking chemical waste water also acts on height separately than Zero-valent Iron, ultrasonic wave.The BOD of final outflow water
5/ COD brings up to 0.36 by original 0.08, and the biodegradability of waste water also obtains to significantly improve.And the colourity that Zero-valent Iron acts on separately, ultrasonic wave acts on waste water separately reduction is not very remarkable.
Difference from Example 1 is: 1.0L waste water and 100g zeroth order iron powder are joined in the reactor, and wherein the physical properties of Zero-valent Iron is: micron order iron powder, its purity are 99%, and particle diameter is 0.04mm, and specific surface area is 1.0m
2/ g; Adopting hydrochloric acid to regulate pH to 1.0, is stirring reaction 20min under 160W, the 50 ℃ of temperature at ultrasonic power then, realizes that waste water decoloring and COD remove (decolorizing effect is referring to table 2).
| The zeroth order iron/ultrasonic wave synergistic reaction is to coking waste water decoloring effect | ||||||
| System/project | Water inlet COD | Water outlet COD | Water inlet colourity | Effluent color dilution | Water inlet BOD 5/COD | Water outlet BOD 5/COD |
| (mg/L) | (mg/L) | (doubly) | (4 times) | |||
| Zero-valent Iron+ultrasonic wave | 3240 | 960 | 1500 | 100 | 0.08 | 0.38 |
Find out that by table 2 improve temperature of reaction, Zero-valent Iron consumption, ultrasonic power and reduce the decolorizing effect that initial pH on wastewater can improve waste water: the chroma in waste water after the processing only is 100, and its BOD
5/ COD value brings up to 0.38, and promptly biodegradability obtains to significantly improve.
Difference from Example 1 is: 1.0L waste water and 2g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is a nano grade iron powder, and its purity is 99%, and particle diameter is 100nm, and specific surface area is 70m
2/ g; Adopting hydrochloric acid to regulate pH to 6, is stirring reaction 120min under 200W, the 10 ℃ of temperature at ultrasonic power then, realizes that waste water decoloring and COD remove.
Difference from Example 1 is: 1.0L waste water and 100g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is the micron order iron powder, and its purity is 99%, and particle diameter is 0.1mm, and specific surface area is 0.7m
2/ g; Adopting hydrochloric acid to regulate pH to 5, is stirring reaction 5min under 180W, the 60 ℃ of temperature at ultrasonic power then.
Difference from Example 1 is: 1.0L waste water and 150g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is a nano grade iron powder, and its purity is 99%, and particle diameter is 60nm, and specific surface area is 150m
2/ g; Adopting hydrochloric acid to regulate pH to 4, is stirring reaction 15min under 190W, the 20 ℃ of temperature at ultrasonic power then.
Embodiment 6
Difference from Example 1 is: 1.0L waste water and 200g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is a nano grade iron powder, and its purity is 99%, and particle diameter is 60nm, and specific surface area is 150m
2/ g; Adopting hydrochloric acid to regulate pH to 4, is stirring reaction 15min under 190W, the 20 ℃ of temperature at ultrasonic power then.
Embodiment 7
Difference from Example 1 is: 1.0L waste water and 500g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is a nano grade iron powder, and its purity is 99%, and particle diameter is 60nm, and specific surface area is 150m
2/ g; Stirring reaction 50min under ultrasonic wave, 70 ℃ of temperature.
Embodiment 8
Difference from Example 1 is: 1.0L waste water and 400g zeroth order iron powder are joined in the reactor, and Zero-valent Iron is a nano grade iron powder, and its purity is 99%, and particle diameter is 80nm, and specific surface area is 90m
2/ g; Stirring reaction 80min under ultrasonic wave, 70 ℃ of temperature.
In actual application, parameters such as ultrasonic power, reaction pH, temperature, Zero-valent Iron consumption can be undertaken preferably by economic and practical principle.
Claims (4)
1. method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction to waste water decoloring, it is characterized in that: waste water and zeroth order iron filings/powder are joined in the reactor, be stirring reaction 1-120min under the ultrasonic wave effect of 150-200W at power, realize that waste water decoloring and COD remove; The usage quantity of zeroth order iron powder is to add Zero-valent Iron 2-500g in every liter of waste water.
2. by the described method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction to waste water decoloring of claim 1, it is characterized in that: described temperature of reaction is 10-80 ℃.
3. by the described method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction to waste water decoloring of claim 1, it is characterized in that: the initial pH on wastewater value adopts hydrochloric acid to be adjusted to 1-6.
4. by the described method of utilizing the zeroth order iron/ultrasonic wave synergistic reaction to waste water decoloring of claim 1, it is characterized in that: described Zero-valent Iron is an iron powder, and it can be micron order iron powder or nano grade iron powder, micron order iron powder purity＞99%, particle diameter is 0.02～0.10mm, and specific surface area is 0.7～1.0m
2/ g; Nano grade iron powder, its purity＞99%, particle diameter are 30～100nm, specific surface area is 70～150m
2/ g.
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| CN102276045A (en) * | 2010-06-11 | 2011-12-14 | 南京宏德纳米材料有限公司 | Method for treating typical heavy metals and organochlorine waste water by using nano zerovalent iron as initiator |
| CN102774952A (en) * | 2012-07-27 | 2012-11-14 | 黑龙江建龙钢铁有限公司 | Method for treating coking wastewater |
| CN102795690A (en) * | 2012-08-24 | 2012-11-28 | 四川大学 | Wastewater treatment method by ultrasonic reinforcement micron-scale iron-copper bimetallic particle |
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